Manufacture of improved filaments, threads, foils, or sheets of cellulose esters or ethers



Patented July 29, 1941 UNITED, STATES PATENT OFFICE THREADS, FOILS, ORSHEETS OF CELLU- LOSE ESTERS OR ETHERS John Gwynant Evans and ArnoldShepherdson, Manchester, England, assignors to Inrpenal ChemicalIndustries Limited, a corporat on of Great Britain No Drawing.Application March 2a, 1938, Serial A 13 Claims.

This invention relates to the manufacture of improved filaments,threads, foils or sheets of cellulose esters or ethers.

In the manufacture of filaments, threads, foils or sheets of celluloseesters or ethers it is customary, to extrude' a spinning solution, whichcomprises a solution'of the said esters or ethers in suitable organicsolvents together with suitable softeners, plasticisers, or otheringredients as necessary, through a suitably shaped orifice so that thesolvents are volatilised from the extruded mass as in the dryspinningprocess, or so that the extruded. mass is coagulated in a coagulatingbath, as in the wet spinning process. The drying atmosphere iii theformer case and the coagu- In Great Britain March 31, 1937 lating bathin the latter case may both be ,re-

garded as setting media for the extruded mass.

The extruded mass may or may not be subjected to tension whilst it isstill in a plastic condition.

For convenience, the filaments, threads, foils or sheets thus producedwill hereinafter bereferred to generically as cellulosic shapedmaterial, bearing in mind that the cross-section of the resultingfilament, thread, foil or sheet etc. is determined and shaped by theoutline of the orifice employed and subsequent tension treatment whereemployed.

According to thepresent invention we incorporate into the spinningsolutions of the kind referred to a quaternary ammonium salt ashereinafter defined and, having formed filaments, threads, foils orsheets by wet or dry spinning of a. carbamate, for instance, the residueof methyl carbamate,

the group N(tert) may represent the residue of a tertiary aliphaticbase, or may stand for the residue of a heterocyclic base, such aspyridine or quinolineifinally, the symbol.Y stands for the monovalentanion of an acid, for instance,

used in the process of the invention there may 1 be mentioned, forexample, octadecyloxymethylpyridinium chloride,octadecyloxymethylpyridinium bromide, octadecyloxymethylpyridiniumiodide; octadecyloxymethylpyridinium nitrate,

in the customary manner, we subject the said filaments, threads-toils orfilms to a heat treat ment at temperatures above 70 C.

The quaternary ammonium salts to be used according to the presentinvention are compounds of the general formulai RX--CH2N(tert) Y,wherein R is a long-chain aliphatic radical, having not less than 12carbon atoms, it may, however, be a saturated or unsaturated hydrocarbonradical; also, it may be the radical of a long chain'carboxylic acid, i.e. of what is commonly' known as a fatty acid in the originaletymological sense, that 15,112 may have the form R'-C0, wherein R is analiphatic hydrocarbon radical of not less than 11 carbon atoms; X is acarbon-to-carbon linking member and maybe oxygen, sulphur, or an iminoor substituted imino group. Among the substituted imino groupspyridinium may be mentioned alkylimino, such as methylimino orethylimino; acylamido, such' as acetimido, aralkylimino, such asbenzylimino;

octadecyloxymethylpyridinium a ci d oxalate,

cetyloxymethylpyridinium p y r i din e sulphite,

- cetylthiomethyl pyridinium bromide, octadecyloxymethyltriethylammoniumchloride, octadecyloxymethyltriethanolammonium chloride,octadecyloxymethylquinolinium chloride; pyridinium derivatives from thechloromethyl ethers .of-

sperm oil alcohols, lauramidomethylpyridinium' chloride,stearamidomethylpyridinium chloride, stearamidomethylpyridiniumbromide,. stearamidomethylpyridinium nitrate, stearamidomethylpyridiniumpyridine sulphite, stearamidomethylm-nitrobenzene sulhonate, N-methyl-stearamidomethylpyridinium chloride,

stearanilidomethylpyridinium chloride; oleylamidomethylpyridiniumchloride, N-carbomethoxyheptadecylaminomethylpyridinium eh i o r 1 lie,p-cetylphenylaminomethylpyridinium pyridine sulphite, andp-stearamidophenylaniinomethylpyridinium pyridine sulphite. V

The defined quaternary ammonium salts are soluble in many of thesolvents commonly used for the making up of spinning solutions such as,for example, acetone, mixtures of acetone and methyl formate, methylorethyl acetates,

acetylacetone or diacetone alcohol. Thus the quaternary salts mayconveniently-be incorporated by dissolving in the already made spinningarylimino, such as anilino; and finally, the residue solution or,preferably, by dissolving the salts in a suitable solvent and admixingwith the already made spinning solution or with one or more of theingredients thereof before making up the spinning solution. Thequaternary salts may be incorporated if desired in the form ofsuspensions or dispersions in a suitable liquid medium provided that thesolid particles in the said sus-= pensions or dispersions are not solarge that they block or foul the spinning orifice.

Filaments, threads, foils or sheets made in accordance with the presentinvention are characterised by theirwater-repel1ent properties. Further,the filaments, threads or woven fabrics made therefrom have a remarkablesoftness of handle. The water-repellent properties and soft handle areresistant to laundering and dry-cleanmg.

The invention is illustrated but not limited by the following examples,in which the parts are by weight.

' Example 1 To 1000 parts of a 25% solution of cellulose acetate in amixture of 950 parts of acetone and 50 parts of water, there is added1000 parts of acetone containing 5 parts of stearamidomethylpyridiniumbromide (which may be prepared by reacting pyridine withstearamidomethyl bromide; see British specification No. 471,130).Theresulting spinning solution is forced through a spinning nozzle intoa current of warm air in the known manner. The filaments so formed are,when dry, subjected to a dry heat for 10 minutes at 120 C. The resultantfilaments have water-repellent properties which are resistant to washingand dry cleaning treatments.

, Eaiample 2 Tea solution of 200 parts of commercial cellulose acetatein 800 parts of a mixture of acetone and water (96% acetone, 4 partswater), there are added 4 parts of octadecyloxymethylpyridinium chloridedissolvedin 46 parts of ethanol. This solution is extruded throughspinning dies in the usual manner into a warm atmosphere of acetonevapour and the threads thus formed are freed from solvent by drying in acurrent of Warm air,

The dried threads are now heated for 2 minutes at 150 C. The threads soobtained are water-repellent and are softer than threads similarly spunfrom solutions containing no octadecyloxymethylp'yridinium chloride. Thewaterrepellent properties are resistant to washing and to dry-cleaningtreatments.

Example 3 To a solution containing 150 parts of commercial cellulose.acetate dissolved in 850 parts of a mixture of acetone and water (95%acetone, 5% water), there are added 3 parts of the mixed pyridiniumchlorides derived from the chloromethyl ethers of sperm oil alcoholscontained in 47 parts of-acetone.

This solution is extruded and the threads are dried. and heated asdescribed in Example 2.

After the heat treatment the threads are im-' ing folds. Theseproperties are resistant to washing and dry-cleaning treatments.

Example 4 To 50 parts of commercial cellulose acetate dissolved in 900parts of acetone there are added 2 parts of stearamidomethylpyridiniumnitrate dissolved in 48' parts of warm ethanol. This solution isextruded into a 23% aqueous solution of calcium chloride and the threadsthus formed are dried rapidly at 50-60 C. in .a current of Warm air. Thedry threads are then heated at C. for 10 minutes.

After the heat treatment the threads are immersed for a few minutes at40 C. in a solution containing 0.5 part of 'oleyl sodium sulphate and 1part of ammonia per 1000 parts of water. The

threads are well rinsed and dried.

Threads thus treated are water-repellent and very much softer thanthreads formed in the absence of the stearamidomethylpyridinium nitrate.

These properties are resistant to Washing and dry-cleaning processes.

In the above example suitable additions may be made to the spinningsolution or to the coagulating bath to assist in the production ofuniform homogeneous fibres. For instance, benzene and alcohol orpyridine or aniline may be added to the spinning solution, or thecoagulating solution may contain thiocyanates or water soluble solventsor swelling agents for cellulose acetate, such as acetone, di-acetonealcohol or ethanol.

Example 5 To 100 parts of cellulose formate (formyl content 20%)dissolved in 900 parts of acetone there are added 3 parts ofoctadecyloxymethylquinolinium bromide dissolved in 47 parts of ethanol.The solution is extruded into a 23% solution of calcium chloride and thethreads thus formed are dried rapidly in a current of warm air at 4050C.

The dry threads are heated for 10 minutes at C. and are then washed asdescribed in the preceding example.

The threads produced-are highly wateflrepellent and considerably softerthan threads of cellulose form-ate, made in the absence ofoctadecyloxymethylquinolinium bromide. T h e s e properties areresistant 'to washin and to drycleaning treatments.

Example 6 To 50 parts of acetone soluble ethyl cellulose dissolved in950 parts of acetone there-are added 1 part of cetyloxymethylpyridiniumpyridine sulphite and 0.1 part of hexamethylene tetramine dissolved in49 parts of ethanol. This solution is extruded into an atmosphereofacetone vapour at a temperature of 40-50" C.

The threads of ethyl cellulose thus formed are freed from acetone bydrying in a current of warm air and are thenheated for 2 minutes while Yis the anion of a water-soluble acid; then" We claim:

1. The process of. imparting water-repellency and softnesscharacteristics to cellulosic shaped material of the class formed byextrusion molding from cellulosic raw material of the group consistingof cellulose esters and cellulose ethers, which comprises incorporatinginto a solution of said raw material, in an organic solvent, aquaternary ammonium compound of the general at a temperature not lessthan 70 C.

\ 2. The process of imparting water-repellency and softnesscharacteristics to cellulosic shaped material of the class formed byextrusion mold- .ing from cellulosic raw material of the groupconsisting of cellulose esters and cellulose ethers,

which comprises incorporating into a solution of said raw material, inan organic solvent, a quaternary ammonium compound of ,-the generalformula RCONHCI-hN(tert)-Y, wherein R is a long-chain aliphatichydrocarbon radical having not less than,11 carbon atoms, N(tert)represents the molecule of a tertiary organic base,while Y is the anionof a water-soluble acid; then subjecting said solution to extrusion andsetting to form shaped material, and finally subjecting said formedmaterial to heat treatment in the absence of moisture at a tempera turenot less than 70 C.

3. .The process of imparting water-repellency and softnesscharacteristics to cellulosic shaped material of the class formed byextrusion molding from cellulosic raw material of the group consistingof cellulose esters and cellulose ethers, which comprises incorporatinginto a solution of said raw material, in an organic solvent, a quaternary ammonium compound of the general formula wherein R is a loweralkyl radical, R is a longchain aliphatic hydrocarbon radical having notI less than 12 carbon atoms, N(tert) represents the molecule of atertiary organic base, while Y is "the anion of a water-soluble acid;then subjecting said solution to extrusion and settingto form shapedmaterial, and finally subjecting said formed material-to heat treatmentin the absubjecting said solution to extrusion and setting to formshaped material, and finally subjecting said formed material to heattreatment in the absence of moisture at a temperature not less than 70C.

5. The process of imparting water-repellency and'softnesscharacteristics to cellulosic shaped material of the class formedbyvextrusion molding from cellulosic raw material of the groupconsisting of celluloseesters and cellulose ethers,

which comprises incorporating into a solution of said raw material, inan organic solvent, a quaternary ammonium compound of the generalformula wherein R is a long-chain aliphatic hydrocarbon radical havingnot less than 11 carbon atoms, while Y is the anion of a water-solubleacid; then subjecting said solution to extrusion and setting toformshaped material, and finally subjecting said formed material to heattreatment in the absence of moisture at a temperature not less than 70C.a j 6. The process of imparting water-repellency and softnesscharacteristics to cellulosic shaped material of the class formed byextrusion mold-' ing from cellulosic raw" material of the groupconsistingof cellulose esters and cellu]oseethers,'

which comprises incorporating into a solution of said raw material, inan organic solvent, a quaternary ammonium compound of the generalformula wherein R is a long-chain aliphatic hydrocarbon radical havingnot less than 12 carbon'atoms,

while Y is the anion of a water-soluble acid; then subjecting saidsolution to extrusion and setting to form shaped material, and finallysubjecting said formed material to heat treatment in the absence ofmoisture at a temperature not less than 70 C.

v7. The process of improving the feel and wa-.

ter-repellency characteristics of cellulose acetate textile material,which comprises forming a sosence of moisture at a temperaturenot lessthan 4. The process of imparting water-repellency and softnesscharacteristics to cellulosic shaped material of the classformed byextrusion molding from cellulosic raw material of the group consistingof cellulose esters and cellulose ethers, which comprises incorporatinginto 'asolution of said raw material, in an organic so1ve1'1t,'aquaternary ammonium compound of the general formula R-0CHaN(tert).-Y,wherein R is a long-chain aliphatic hydrocarbon radical having not lessthan 12 carbon atoms, N(tert) represents the molecule of a tertiaryorganic base,

lution of cellulose acetate in acetone, incorporating into said solutionfurther a stearamidomethyl pyridinium' salt of a water-soluble acid,then subjecting the solution to extrusion and setting to form a shapedtextile material, and nnally subjecting said textile material to heattreatment in the absence of moisture at'a temperature between and C.

8. Artificial cellulosic material of the grou consisting of filaments,threads, foils and sheets of cellulose esters and of cellulose'ethers,char acterized by having a water-repellent surface, said material havingincorporated within its body the reaction product obtainable by heat ingin contact with said cellulosic material but in theahsence ormoistureandatatemmraturcbetween 120 and 150 0., a quaternary ammoniumcompound of the general formula R-X-CHz-N (tert) -Y,

radicals having not less than 12 carbon atoms, X

is a carbon-to-carbon linking member selected from the group consistingof oxygen, sulfur and the imino radicals, N(tert) represents themolecule of a tertiary organic base, while Y is the anion of awater-soluble acid. I

9. Artificial cellulosic shaped material characterized by having a softfeel and a water-repellent surface, said material being the product of aprocess as defined in claim 6.

10. Artificial cellulosic shaped material characterized by having a softfeel and a water-repellent surface, said material being the product of aprocess as defined in claim '7.

11. Artificial cellulosic shaped material char-'- acterized by having asoft feel and a water-repellent surface, said material being the productof a process as defined in claim 8.

12. Artificial cellulosic textile material of the group consisting ofcellulose esters and cellulose ethers, characterized by having a softfeel and a water-repellent surface, said material having incorporatedwithin its fiber the reaction product obtainable by heatingstearamido-methyl-- rial of the class formed by extrusion molding froman organic solution of a compound of the group consisting ofcellulose-esters and of cellulose. ethers, said material includingwithin its structure a substantially homogeneous combination of the saidcellulosic material with a water-repellency agent of the group havingthe general formula R-XCH2N(tert)-Y, wherein R is a long-chain aliphaticradical selected from the group consisting of aliphatic hydrocarbonradicals and aliphatic hydrocarbon acyl radicals having not less than 12carbon atoms, X is a carbon-to-carbon linking member selected from thegroup consisting of oxygen, sulfur, and the imino radicals, N(tert)represents the molecule of a tertiary organic base, while Y is the anionof a water-soluble acid.

JOI-IN GWYNANT EVANS.

ARNOLD SHEPHERDSON.

